DE4122473A1 - METHOD FOR DEPOSITING TITAN, ZIRCONIUM OR HAFNIUM CONTAINING LAYERS - Google Patents

Description

The invention relates to a method for Ab separation of a titanium, zirconium or hafnium containing Layer on a substrate.

It is known to coat substrates by surface coating to modify so that their surface determined has functional properties. For example to conduct or conduct electricity Layers, e.g. B. Apply conductor tracks. Furthermore it is known, mediating or preventing migration Apply layers on substrates.

The object of the present invention is a Ver drive to deposit a titanium, zirconium or hafnium Specify containing layer on a substrate. These The object is achieved by the method according to the invention.

The inventive method for the deposition of a Titanium, zirconium or hafnium containing layer A substrate is characterized in that Decomposition of a compound of general formula (I)

(C _n R¹ _u R² _v ) Mt (C _m R³ _w R⁴ _x ) (I)

wherein

n, m = 5, 6, 7, 8
u + v = n
w + x = m and
R¹, R², R³ and R⁴ are the same or different and are hydrogen or alkyl, especially methyl,
Mt means titanium, zirconium or hafnium, preferably titanium,

a layer containing titanium, zirconium or hafnium the substrate. u, v, w and x correspond to whole Numbers between o and n or m.

The ligands of the compounds of formula (I) are carbon rings. The connections are usually in the form of so-called "sandwich" connections. In them, the ring carbon atoms of the carbon rings C _n R¹ _u R² _v and C _m R³ _w R⁴ _{x are} generally coordinated in the same way on the metal atom. Such carbon rings, which have n or m carbon atoms coordinated in the same way to metal atoms, are also referred to as n-hapto or eta ⁿ or m-hapto or eta ^m . It is generally believed that the compounds of formula (I) exist as (n-hapto-C _n R 1 _u R 2 _v ) Mt (m-hapto-C _m R 3 _w R⁴ _x ).

In the method according to the invention, however, verbs are also used extensions of formula (I) can be used, their cyclic ligands have a slightly different kind of coordination. For the compound (C₈H₈) Ti (C₈H₈) for example is possible Lich held that they are in the form of (8-hapto-C₈H₈) Ti (8-hapto-C₈H₈) or as (8-hapto-C₈H₈) Ti (4-hapto-C₈H₈) is present. Of course (C₈H₈) Ti (C₈H₈) is completely independent of the type of coordina tion usable in the inventive method.

The present invention is made in view of the preferred embodiment, namely the production of titanium containing layers, explained further.  

It is preferred to use compounds in which R¹, R², R³ and R⁴ are hydrogen or in which R¹ and R² is methyl and R³ and R⁴ are hydrogen.

Preferably n and m each mean 8, or else it means n = 5 and m = 7, or it means n = 5 and m = 8, or it n and m each mean 6. Connections are particularly good suitable in which n = 5 and m = 7.

For example, (C₈H₈) ₂Ti; (C₅H₅) Ti (C₈H₈), (C₅Me₅) Ti (C₈H₈); (C₅H₅) Ti (C₇H₇); C₅Me₅) Ti (C₇H₇) or (C₆H₆) ₂ Ti.

It is extremely suitable (5-hapto-C₅H₅) Ti (7-hapto-C₇H₇).

Can be used to deposit a layer containing titanium the skilled person separates from the condensed phase or from the gas or vapor phase. For the subject It goes without saying that he is not just one certain compound of general formula (I), but can also use mixtures of such compounds.

For separation from the condensed phase the person skilled in the art the compound of formula (I) without a solution medium or preferably dissolved in a solvent on the substrate and decomposes the compound. As a solution agents can be polar or non-polar, aprotic organic Solvent, the coordinating property if desired Shafts can be used. Are suitable for example aliphatic hydrocarbons such as pentane or petroleum spirit, aromatic hydrocarbons such as Benzene or toluene or ether such as tetrahydrofuran.

To the respective output connection on the substrate to apply, one can use known methods, for example you can put the substrate in the compound or immerse a corresponding solution, you can do that  Starting compound or a corresponding solution on the Spread substrate or, preferably, the compound or spray an appropriate solution onto the substrate.

By means of this embodiment of the invention Process, namely the application of the starting compound (or a corresponding mixture of starting compounds gen) from the condensed phase, even large ones succeed Coating surfaces very quickly.

Then the decomposition takes place on the substrate brought starting compound for the deposition of a titanium containing layer, if desired under reduced Print. The decomposition is expediently brought about thermally.

This can be done by introducing the output ver bond coated substrate in a corresponding heated chamber, by heating the substrate before while and / or after the application of the starting compound the specified temperature range.

Thermal decomposition can also be radiation-induced gracefully caused, for example by a laser, that in the UV range, in the infrared range or in the range of visible light works and heats up the wearer.

If desired, the decomposition can also be caused by Photolysis take place. The photolytic decomposition can but also by one at the corresponding wavelength operated laser or a UV lamp.

The decomposition can also be induced by plasma to lead. The various known Ver drive.

For example, a thermal plasma process ren, e.g. B. arc plasma or plasma jet apply. The  The pressure is usually between 10 Torr and normal print.

Low-pressure plasma processes are also particularly suitable, for. B. DC plasma process, glow discharge plasma process and AC plasma process, e.g. B. low-frequency, medium-frequency, high-frequency plasma processes and microwave plasma processes. It is usually carried out at pressures below 10 mbar, for example between 10 ^-2 and 1 mbar.

The plasma-induced decomposition takes place in known ones Plasma reactors. For example, pipe, Tunnel, parallel plate and corona discharge reactors. Since the decomposition in plasma if desired at low Temperatures can be carried out is the decomposition in the Plasma well suited for coating substrates with ver relatively lower thermal stability, for example for Coating of plastics.

The person skilled in the art can add a reactive gas Form in which the titanium is present in the layer rivers. This, as well as the possibility of simultaneous Deposition of other metals or successive separation formation of further, in particular further layers with others Composition, will be explained.

Another embodiment of the invention The process relates to the decomposition of the starting compound in the gas or vapor phase. This embodiment enables if the deposit adheres particularly well, evenly thick, thin layers.

The pressure in the vapor phase or gas phase can be more or less high. For example, you can work at a pressure that corresponds to the vapor pressure of the starting connection used at the working temperature. The total pressure can also be higher up to normal pressure. It is expedient to work at reduced pressure, for example at 10 ^-2 to 10 mbar, preferably at 0.1 to 1 mbar.

The decomposition of the starting compound in the steam phase or gas phase is advantageously carried out in the manner of a CVD (Chemical Vapor Deposition) process.

The basic procedure for coating Substrates using CVD processes as well as suitable Neter equipment for this are known. EP-A 2 97 348 (which, however, have completely different coatings summarizes as the present invention, namely with the Ab separation of copper, silver or gold containing Layers) gives the expert detailed information on how a CVD process is to be carried out and what equipment are usable.

The decomposition from the gas or vapor phase is Appropriately in a pressure-resistant, evacuable device carried out. In this device that is to be coated ting substrate introduced. At reduced pressure creates an atmosphere containing the titanium Contains parent compound. In addition to the under these Bedin gaseous or gaseous output compound can, if desired, inert gas or reactive gas be present in the gas space of the device.

In a variant, the starting connection is combined men with the substrate to be coated in the device brought in.

In an alternative, preferred variant, to next, just insert the substrate into the flameproof device brought and the already gaseous or vaporous Continuous output connection via a special line Lich or discontinuously in the device brings. A carrier gas can also be used here.  

The conversion of the starting compound into the gas or vapor phase can be done by heating and desired if support by adding a carrier gas.

The decomposition takes place according to known methods ther mixed, plasma-induced and / or photolytic.

The thermal decomposition from the gas or steam phase is usually carried out so that the walls of the Device should be kept cold and the substrate on a Temperature is heated at which the desired Titanium-containing layer deposits on the substrate. The Experts can do simple tests for the connection used in each case the necessary minimum easily determine temperature. Usually that lies Temperature to which the substrate is heated above of about 120 ° C.

The substrates can be heated in a conventional manner take place, for example by resistance heating, induct tion heating, electric heating device such as heating coils or similar. The substrates can also be heated can be induced by radiation energy. Suitable for this especially laser radiation energy. For example you can use lasers that are in the visible range Light, work in the UV range or in the IR range. laser have the advantage that you can more or less can focus and therefore targeted certain, limited Can heat areas or points of the substrate.

Since the thermal CVD process is usually used for Vacuum is carried out, it is for the expert of course, to provide pressure-resistant equipment, such as they are used in vacuum technology. The apparatus expediently have heatable gas lines for the organometallic compound or the inert gas, lockable Openings for gas inlet and outlet, open if necessary  solutions for supplying a carrier or reactive gas, Temperature measuring devices, an opening if desired for the supply of the organometallic compound, a Device for heating the substrate, one for Generation of the desired vacuum suitable pump etc. In the event of carrying out radiation Energy-induced CVD process must also have one Radiation source to be present, the radiation in the area visible light, infrared or ultraviolet Area. Corresponding ones are particularly suitable Laser radiation energy sources. By means of the radiation The substrate can be heated.

A very simple, practical device for performing the procedure is shown in FIG. 1.

It comprises a glass tube 3 connected to an inert glass feed line 1 via a shut-off valve 2 , which is arranged concentrically in a tubular heating furnace 4 which has two heating zones 5 and 6 ("two-zone tube furnace"). The other side of the tube is connected to a vacuum pump 8 via a cold trap 7 .

In the first heating zone, which is on the side of the inert glass supply line, the output connection is switched on brings. In the second heating zone, which is on the side of the Vacuum pump lies, you bring the substrate.

The plasma-induced decomposition is carried out in one apparatus described above.

Without an explanation for the formation of Layers given by decomposition of the titanium compounds should be assumed that gases or vapors of the Titanium compound get on the substrate and there under Formation of the titanium-containing layers are decomposed. The thickness of the layer is essentially dependent on that Time period during which the deposition was carried out  is the partial pressure of the organometallic compound and the deposition temperature. There can be more or create less thin layers, for example Layers up to 20 microns thick for example between 100 angstroms and 20 micrometers. Each according to the desired layer thickness, the person skilled in the art can orienting experiments to produce a titanium ent holding layer of certain thickness necessary time and determine the deposition temperature.

As already said, the decomposition can also be photoly table can be effected, for example by using one suitable wavelength working laser used or using a UV lamp.

The gas space surrounding the substrate contains the gas or vaporous starting compound. It was already mentioned above that an inert gas continues or a reactive gas can be contained in the gas atmosphere can. Depending on the type of implementation, be whole different layers containing titanium are deposited.

If the starting compound is decomposed without the addition of a Inert gas or a reactive gas, so differ thermal decomposition, especially when performing As a CVD process, layers that are essentially titanium contained in metallic form.

Do you work without adding an inert gas or one Reactive gas and causes the decomposition plasma induced in a CVD process, layers separate that contains the titanium essentially in the form of titanium carbide ten.

Layers that are particularly affected by thermal decomposition mainly in a thermal CVD process lichen in metallic form or layers, which in particular in a plasma-induced CVD process  ren the titanium essentially in the form of titanium carbide hold will also be deposited if you are present an inert gas, for example in the presence of noble gases like argon works.

In another embodiment, the Zer is performed enforcement in a reactive gas atmosphere. Such reactive gas atmosphere can of course additionally inert gas contain, for example noble gases such as argon.

In one variant, one works in a nitriding the reactive gas atmosphere. The decomposition is particularly widespread especially in the manner of a thermal or plasma-induced CVD process through. Contain the decomposition of the titanium the starting compound in a reactive gas atmosphere, which ammonia, nitrogen or similar N-containing Zu sets contains results in titanium-containing layers, which the titanium essentially in the form of titanium nitride ten.

In another variant, the decomposition is carried out in particular in the manner of a thermal or plasma-induced CVD process. By decomposing the titanium-containing starting compound in a reactive gas atmosphere, the N-containing gas additives and C-containing gas additives, e.g. B. contains alkanes, form layers that hold the titanium essentially in the form of titanium carbonitride, TiC _x N _y , ent. In the carbonitrides, the sum of x and y is approximately 1 to 1.1. These compositions can also be non-stoichiometric.

In another variant, the decomposition is carried out also particularly in the manner of a thermal or plasma-induced CVD process and decomposes the Starting compound containing titanium in a hydrolysy rendering and / or oxidizing reactive gas atmosphere. This reactive gas atmosphere expediently contains water and / or oxygen, N₂O or ozone. Form during decomposition  layers that are essentially in the form of titanium Contain titanium dioxide.

In principle, in the method according to the invention coat any substrates on which a coating tion is desirable. For example, anorga African materials such as metals or metal alloys such. B. Steel, semiconductors, silicon, insulators, ceramics, or organic polymers, e.g. B. polyphenylene sulfide, polyimides or polymethyl methacrylate, as substrates.

The deposition of layers that the titanium in essentially contained in the form of metallic titanium, he not possible, for example, under cover of certain Areas to be coated according to the structure known per se Turierungverfahren the generation for the electrical Electrically conductive tracks on non-conductive substrates ten, for example on ceramic or organic polymers ren. On certain substrates one observes under be agreed prerequisites known diffusions phenomena. Metallic titanium applied to silicon substrates, diffuses when the substrates are heated high temperature, for example 700 ° C in this silicon substrate and forms layers that more or less Contain titanium and represent titanium silicide in the limit case. Such titanium silicides are functional layers in the Microelectronics.

Layers that are essentially in the form of titanium Contain titanium carbide, titanium nitride and / or carbonitride, reduce wear and improve adhesion. Example wise you can coat metals or metal alloys, especially those used to manufacture tools or machine components are used. Continue to work Layers containing titanium nitride as diffusion barrier, that is needed, for example, in semiconductor technology the.  

Layers containing titanium dioxide are exemplified wise in the optical industry to make plastics scratch-resistant.

The method according to the invention offers the person skilled in the art but other options. It is suitable, for example also for the deposition of layers, which besides the Titan contain one or more other metals. These Embodiment of the method according to the invention is there characterized in that one for the separation of such Layer one or more compounds of other metals and a compound of the general formula (I) at the same time decomposed. Then layers, the titanium and one or more other metals in a homogeneous mixture hold. In this embodiment, too work inert or reactive gas atmosphere. For example a β-Di can be used as a compound of another metal Use lead ketonate in an oxidizing atmosphere Deposit layers containing lead titanate. Such Layers have dielectric properties.

Furthermore, the expert can do several different Apply layers successively on substrates gene, wherein at least one layer according to the Invention method is generated.

For example, you can on a substrate after inventive method first a titanium nitride ent deposit the holding layer, which acts as a diffusion barrier acts and also the liability of others to be deposited Layers improved. Then you can after the fiction procedures by appropriate coverage of certain not Areas to be coated according to a structure known per se production process by using metal layers containing titanium according to the Invention separates according to the procedure. If you want, you can then again a layer containing titanium nitride after the deposit the inventive method as a protective layer.  

Of course you can before or after the separation of Titanium-containing layers according to the invention Process also known deposition processes perform. For example, you can follow on substrates the process according to the invention contains a titanium nitride layer as a diffusion barrier and for adhesion generate improvement. Then you can according to the from the EP-A 2 97 348 known methods under suitable cover certain areas not to be coated known structuring methods conductor tracks generate by decomposing trialkylphosphane (Cyclopentadienyl) copper (I) complexes in a ther mix copper CVD process at greatly reduced pressure separates.

The Ver used in the inventive method bonds of the general formula (I) and their preparation are already known.

To prepare compounds of the general formula (I) in which n is 5 and m is 7 or 8, it is possible to start from compounds of the general formula (C₅R¹ _u R² _v ) TiCl₃ (II). The production of these intermediate compounds is known and is described for example in the "Gmelin Handbook of Inorganic Chemistry, Supplement to the 8th Edition, Volume 40, Titanium-Organic Compounds, Part 1, Pages 136 to 142". For example, titanium tetrachloride can be reacted with the corresponding cyclopentadienyl lithium, magnesium or sodium compound with or without a solvent and the compound of the formula (II) isolated.

For example, the production of (C₅H₅) TiCl₃ by reacting titanium tetrachloride and Bis (cyclopentadienyl) magnesium in xylene with a 78% yield prey.  

The production of (C₅H₄Me) TiCl₃, wherein "Me" is methyl means done by the reaction of titanium tetrachloride with methylcyclopentadienyl sodium in boiling xylene.

The production of (C₅Me₅) TiCl₃ takes place by order substitution of pentamethylcyclopentadienyllithium in benzene / Hexane at room temperature.

The corresponding can be similarly Prepare zirconium compounds, cyclopentadienyl zir conium trichloride, for example from cyclopentadienyl mag nesium chloride or bis (cyclopentadienyl) magnesium and zir Contetrachloride, see also Gmelin's anorga manual niche chemistry, supplementary work for the 8th edition, zirconium organic compounds, Volume 10 (1973), pages 15 and 16.

Corresponding hafnium compounds can, for example by chlorination of corresponding bis (cyclopenta dienyl) hafnium dichloride compounds are prepared.

The organotitanium, zir Conium or hafnium trichloride compounds then become the desired compounds of the general formula (I) implemented further.

The reaction of (C₅H₅) TiCl₃ to (C₅H₅) Ti (C₇H₇) with cyclopheptatriene in the presence of a Grignard verb dung, namely i-C₃H₇MgBr in ether, is at H.O. van Oven, H.H. De Liefde Meÿer in J. Organomet. Chem. 27 (1970), Pages 159 to 163.

The conversion of (C₅H₅) TiCl₃ to (C₅H₅) Ti (C₇H₇) using Mg and cycloheptatriene in THF or to (C₅H₅) Ti (C₈H₈) using K₂C₈H₈ in THF is from L.B. Kool, M.D. Rausch and R.D. Rogers in J. Organomet. Chem. 297 (1985), pages 289-299.  

The production of (C₅Me₅) Ti (C₇H₇), (C₅Me₅) Zr (C₇H₇), (C₅Me₅) Hf (C₇H₇) and (C₅Me₅) Ti (C₈H₈) and (C₅Me₅) Zr (C₈H₈) is described by J. Blenkers, P. Bruin and J.H. Teuben in J. Organomet. Chem. 297 (1985), pages 61 to 67 described.

According to these authors, the connections are put through Implementation of the relevant organometallic trichloride compound with cycloheptatriene or cyclooctatetraene Mg chips in ether.

Substituted cycloheptatriene can also be used put. Organometallic compounds are then obtained, in which appropriately substituted cycloheptatrienyl Groups exist. The making of such connections gen is, for example, in "Gmelins Handbuch der anorga African chemistry, 8th edition (1984), organotitanium compound gene part 4, pages 82 to 87 ".

The preparation of compounds of general Formula (I), in which n and m is 8, is used as an example by H. Breil and G. Wilke in Angew. Chem. 78 (1966) Page 942. The production succeeds through Um addition of tetrabutoxytitanium with cyclooctatetraene 80 ° C with triethyl aluminum.

The preparation of compounds of the general formula (I), in which n and m each represent 6, can according to the P.N. Hawker, E.P. Kündig and P. Timms in J.C.S. Chem. Comm. 1978, pages 730 and 731. In this process, potassium atoms are converted into a at -100 ° C stirred solution of a titanium halide, e.g. B. TiCl₃ and des desired arens, e.g. As toluene or mesitylene, in tetra hydrofuran condensed. The product then becomes more common Way isolated from solution and crystallized.

Another way of making connections gene of the general formula (I), in which n and m each 6  mean, describe F.W.S. Benfield, M.H. Green, J.S. Ogden and D. Young in J.C.S. Chem. Comm. 1973, Pages 866 and 867. In that process, titanium vapor and benzene vapor in vacuo to the desired (C₆H₆) ₂Ti cocoon densifies.

The following examples are intended to illustrate the invention Explain the procedure further without reducing its scope to restrict.

Example 1 Production of (C₅H₅) Ti (C₇H₇)

The production was carried out in accordance with the working instructions of H.O. by Oven and H.J. de Liefde Meÿer in J. Organomet. Chem. 23 (1970), pages 159 and 160.

8.08 g C₅H₅TiCl₃ and 12.4 g C₇H₈ were under nitrogen atmosphere dissolved in dried, oxygen-free ether. The solution was cooled to -78 ° C and about 140 ml 0.8 molar solution of i-C₃H₇MgBr in ether during one A period of about 4 hours was added. After finished The addition was continued for about 1.5 hours at -78 ° C stirs. The reaction mixture was then left to ambient temperature come and then stirred for about 12 hours long further. The solvent was then removed in vacuo separates, the remaining residue twice with 100 ml each Washed pentane. The remaining residue was then at about 125 ° C and a pressure of about 1 mm sublimated blue crystals. Yield: about 2.8 g.

Example 1 was used to obtain larger amounts of Titanium compound repeated several times.  

2. Application of (C₅H₅) Ti (C₇H₇) for the production of titanium containing layers 2.1. Equipment used

Was used in accordance with Fig. 1 Before direction.

A quartz glass tube was concentric in a 2-zone tube oven introduced. One side of the quartz tube was off lockable connected to one inert gas line, the other Side with a vacuum pump. Between quartz tube and vacuum pump was a freezer trap for separation volatile components from the pumped gas stream.

The organometallic compound to be evaporated was in a porcelain boat in the glass tube in the 1st heating zone of the 2-zone tube furnace. The substrate was placed in the 2nd heating zone. In an attempt the glass wall served as a substrate.

2.2. Test execution 2.2.1. Use of silicon as a substrate

Silicon wafers were used as the substrate. The according Example 1 prepared titanium compound was in the 1st heating zone introduced.

The silicon substrate was in the 2nd heating zone on a Brought temperature of about 400 ° C. The pressure was about 0.03 mbar. The starting compound was in the 1st heating zone heated to 120 ° C. The vapor that forms in the process duct connection flowed over the substrate and decomposed depositing a titanium-containing layer. A Carrier gas was not used.  

After about 10 minutes, the deposition was stopped and the quartz via the inert gas line shut off by then Pipe brought to normal pressure with purified nitrogen. The coated substrates were removed from the quartz tube taken. The analysis showed that the disks with titanium were stratified. The layer contained less than 1% by weight Carbon.

2.2.2. Application of steel from substrate

Example 2.2.1. was repeated, but this time Steel disks were used as the substrate. The disgust conditions of use and the result corresponded to that of example 2.2.1.

2.2.3. Use of glass as a substrate

Example 2.2.1. was repeated. This time, however no substrate introduced into the 2nd heating zone, but the Glass wall in this zone served as the substrate. The rest Implementation corresponded to example 2.2.1. After finished Deposition was found on the quartz glass tube had deposited a layer of titanium.

Claims (16)

1. A method for depositing a layer containing titanium, zirconium or hafnium on a substrate, characterized in that by decomposing a compound of the general formula (I) (C _n R 1 _u R 2 _v ) Mt (C _m R 3 _w R _{w x} ) (I) where, m = 5, 6, 7, 8
u + v = n
w + x = m and
R¹, R², R³ and R⁴ are the same or different and are hydrogen, alkyl, in particular methyl,
Mt titanium, zirconium or hafnium, preferably titanium means a layer containing titanium, zirconium or hafnium on the substrate. 2. The method according to claim 1, characterized in that that either n and m each mean 8, that n = 5 and m = 8, that n = 5 and m = 7 or that n and m are each 6. 3. The method according to claim 1 or 2, characterized records that n = 5 and m = 7 means. 4. The method according to any one of the preceding claims, characterized in that R¹, R², R³ and R⁴ are hydrogen mean or that R¹ and R² methyl and R³ and R⁴ water mean fabric.   5. The method according to any one of claims 1 to 4, because characterized in that the connection of the general my formula (I) decomposed in the liquid phase. 6. The method according to claim 5, characterized in that the compound of general formula (I) on Applies substrate, preferably sprayed, and decomposes. 7. The method according to any one of claims 1 to 4, because characterized in that the connection of the general my formula (I) decomposed in the gas or vapor phase. 8. The method according to claim 7, characterized in that that the compound of general formula (I) under reduced pressure, if desired using a Carrier gas, transferred to the vapor phase and at min decomposed pressure. 9. The method according to any one of the preceding claims, characterized in that the decomposition is thermal causes. 10. The method according to claim 9, characterized in that one can decompose the compound of general Formula (I) thermally by heating the substrate Temperatures above about 120 ° C causes. 11. The method according to any one of the preceding claims, characterized in that the decomposition by means of Radiant energy, especially laser radiation energy causes. 12. The method according to any one of claims 1 to 10, there characterized in that the decomposition plasmaindu gracefully effects.   13. The method according to any one of the preceding claims, characterized in that for the deposition of titanium, Layers containing zirconium or hafnium Titanium, zirconium or hafnium essentially in metal contain the form of decomposition in one opposite the metal formed and the connection used general formula (I) may contain inert hydrogen carries out the gas atmosphere. 14. The method according to any one of claims 1 to 12, there characterized in that for the deposition of titanium, Layers containing zirconium or hafnium Titanium, zirconium or hafnium in the form of nitrides, carbo Contain nitrides or oxides that decompose in property unit of a reactive atmosphere, preferably a nitri dizing, oxidizing, hydrolyzing or carbonizing performing gas atmosphere. 15. The method according to any one of the preceding claims, characterized in that for the deposition of titanium, Layers containing zirconium or hafnium another metal or metals contain one or more compounds of such others Metals and a compound of the general formula (I) decomposed at the same time. 16. The method according to any one of the preceding claims, characterized in that one has several different Deposits layers one after the other.